This is an open access article published under an ACS AuthorChoice License, which permits

copying and redistribution of the article or any adaptations for non-commercial purposes.

Article

Cite This: ACS Omega 2019, 4, 5795−5804 http://pubs.acs.org/journal/acsodf

Effect of the Electronic State of Cu, Ag, and Au on Diesel Soot

Abatement: Performance of Cu/ZnO, Ag/ZnO, and Au/ZnO Catalysts
Grisel Corro,*,† Juan Angel Flores,† Francisco Pacheco-Aguirre,‡ Umapada Pal,§ Fortino Bañuelos,†
Rosalía Torralba,† and Octavio Olivares-Xometl‡
†
Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, 4 sur 104, 72000 Puebla, Mexico
‡
Facultad de Ingeniería Química, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Mexico
§
Instituto de Física, Benemérita Universidad Autónoma de Puebla, Apdo. Postal J-48, 72570 Puebla, Mexico
Downloaded via BENEMERITA UNIV AUTONOMA DE PUEBLA on March 25, 2019 at 19:57:04 (UTC).

*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Noble metals such as Au, Ag, and Cu supported

over semiconducting ZnO are well-known heterogeneous
oxidation catalysts. All of them have been utilized for the
oxidation of diesel soot with varied success. However, Au-
supported ZnO is seen to be superior among them. Here, we
present a comparative study of all these three catalysts for
diesel soot oxidation to explain why Au/ZnO is the best
among them, demonstrating the contribution of electronic
states of metals in composite catalysts. The electronic states of
Cu, Ag, and Au determined by X-ray photoelectron spectros-
copy on 1 wt % Cu/ZnO, 1 wt % Ag/ZnO, and 1 wt % Au/
ZnO catalysts were correlated with their diesel soot oxidation activities. Although all three catalysts present reasonable diesel
soot oxidation activities at relatively low temperature, 1% Cu/ZnO and 1% Ag/ZnO oxidize only about 60% of the deposited
diesel soot around 250 °C and 1% Au/ZnO oxidizes 100% of the deposited diesel soot, at a temperature as low as 230 °C. The
activity of the catalysts is attributed to the formation of stable M0−Mδ+ bifunctional catalytic sites at the metal−ZnO interface,
which enhances the contact efficiency of solid diesel soot on Mδ+ and generates the superoxide species on M0 moieties. The
stability of the bifunctional M0−Mδ+ sites is controlled by the electronic interactions between the metal (M) and n-type
semiconductor ZnO at their interface. Very high activity of 1% Au/ZnO is attributed to the presence of Au3+ at the catalyst
surface, which generates a stronger Coulombic force with diesel soot electrons. We demonstrate a direct relation between the
diesel soot oxidation activity of these three metals and their electronic states at the catalyst surface.

1. INTRODUCTION results in additional fuel consumption and thermal stress to the

There is an increased demand of diesel-powered vehicles in
recent years, owing to their efficient energy conversion, higher
durability, and operation reliability, compared to gasoline-
powered vehicles.1 However, emission of diesel soot from
diesel engines causes severe environmental and health
problems to humans, animals, and plants. The increasingly
stringent U.S. and European emission standards demand a
drastic reduction in the emission of nitrogen oxides and soot
from diesel engines, which requires technical improvements in
the current diesel engines along with improved after-treatment
technologies.
One of the most effective after-treatment technologies for
diesel soot control is based on a diesel soot filter, in which
particles are trapped.2 The filter has to be regenerated
periodically by the combustion of trapped soot. However,
the direct oxidation of soot requires higher temperatures
(around 600 °C) than the highest diesel engine exhaust gas
temperature, which is around 400 °C for most of the diesel
engines.3 Such a high temperature in the filter is generally
attained by injecting a diesel fuel into the exhaust, which
filter.
A catalyzed diesel soot filter is regarded as the best solution
to reduce the soot emissions from diesel engines. In these
filters, soot is trapped and simultaneously oxidized at exhaust
gas temperatures (∼400 °C).4 However, catalytic soot
oxidation is quite slow because of the large size of the soot
particles, which hardly diffuse into the catalyst micropores or
mesopores. Thus, the contact between the catalyst surface and
the soot particles is very low.5 An interesting solution to this
problem is the continuously regenerating trap (CRT), in which
the soot oxidation occurs at relatively lower temperatures.8 In
this technology, NO is first oxidized to NO2 over a platinum
catalyst. NO2 functions as a mobile species, creating a
catalyst−soot contact and lowering the soot oxidation
temperature. However, the use of CRT is severely restricted
Received: November 10, 2018
Accepted: January 22, 2019
Published: March 25, 2019

© 2019 American Chemical Society 5795 DOI: 10.1021/acsomega.8b03142

ACS Omega 2019, 4, 5795−5804
ACS Omega
because of the restriction imposed by diesel engine emission
norms, which demands a strong decrease of NOx emissions.
On the other hand, organometallic fuel additives known as
fuel-borne catalysts (FBCs) can lower the soot oxidation
temperature in soot filters. In this technology, a catalyst-doped
soot is formed during combustion in diesel engines. However,
the application of this technology is strongly restricted because
while the diesel soot oxidation temperature is lowered, the
FBCs are consumed continuously and the catalysts (metal
oxides) are accumulated as ash inside the filter.6,7
Some of the catalysts that show good catalytic performances
in diesel soot oxidation are based on a variety of active
materials such as transition metals, transition-metal oxides,
alkaline metal oxides, perovskites, rare earth oxides, and a
mixture of two or more of them.9−13 One of the main catalytic
functions of transition metals in oxidation reactions is to
transfer the oxygen species from their surface to the
reactants.14 Therefore, the activity of these catalysts for
oxidizing soot particles is the function of their ability to
activate oxygen and the contact probability between the
catalyst and the soot particles.15,18 In other words, these
catalysts must contain active sites for adsorbing and activating
O2 along with active sites for adsorbing diesel soot to generate
close contacts.16,17
In recent studies, we have reported the diesel soot oxidation
activity of group IB metals such as Cu/ZnO, Ag/ZnO, and
Au/ZnO deposited over ZnO.19−21 The activity of diesel soot
oxidation is seen to vary drastically from one catalyst to the
other. While Cu/ZnO and Ag/ZnO present low activity for
diesel soot oxidation, Au/ZnO is seen to be very active for this
reaction at temperatures as low as 230 °C. The unique fact
common for all these three catalysts, noticed through their X-
ray photoelectron spectroscopy (XPS) analysis, is the presence
of both metallic and ionic species at their surfaces. The results
of diesel soot oxidation study of the three catalysts suggest that
the catalytic reactions over them strongly depend on the
electronic states of the supported metals (Cu, Ag, and Au).
The difference in their electronic states is governed through
the differences in the electronic interactions of the metallic
nanoparticles (NPs) with ZnO at their interfaces. In this work,
we present a comparative study, unifying diesel soot oxidation
results of all three catalysts, to demonstrate how the electronic
states of these noble metals control the diesel soot oxidation
behavior of metal−semiconductor nanocomposites. The origin
of different electronic states of the metals at the support
surface has been explained by considering their electronic
interactions with the support ZnO, which is an n-type wide
band gap semiconductor.
2. RESULTS AND DISCUSSION
2.1. Diesel Soot Characterization. Fourier transform
infrared (FT-IR) absorption spectrum of the diesel soot
studied in this investigation is presented in Figure 1. The
spectrum revealed characteristic absorption peaks in the mid-
infrared region. The characteristic signals of C−H symmetric
and asymmetric stretching vibrations of alkane and alkene-type
functional groups appeared at around 2950, 2920, and 2854
cm−1, respectively. The peak detected at around 1711 cm−1
can be assigned to the carbonyl CO stretching in aromatic
and aliphatic aldehydes and ketones. The absorption band
appeared around 1548 cm−1 could be attributed to CC
stretching of aromatics and alkenes. The absorption band
revealed around 1462 cm−1 corresponds to conventional
5796
Article
Figure 1. FT-IR spectrum of the diesel soot collected on reference
ZnO from the combustion vessel exhaust during the burning of diesel
fuel.
coke.22,23 The signal appeared around 1360 cm−1 has also been
observed in activated carbon, graphite, and carbon black.24
The broad signal detected between 1250 and 900 cm−1
might be the result of overlapping of the following peaks: C−O
stretching (1191 and 1070 cm−1), C−O−C stretching (1121
cm−1), and C−C−O stretching.22 The band detected at
around 2360 cm−1 corresponds to CO2 adsorbed on the
catalysts.
2.2. Catalyst Characterization. 2.2.1. Surface Area
Analysis. Specific surface areas (Sg) of the catalysts were
determined from their N2 adsorption−desorption isotherms
recorded at 77 K. The results obtained are summarized in
Table 1. As can be seen, all the freshly prepared catalysts
revealed their very low specific surface area.
Table 1. Texture Properties of the Freshly Prepared
Composite Catalysts
specific surface area average size of metal NPs
catalyst (m2 g−1) (nm)
ZnO 4.52
1% Cu/ZnO 3.31 53.0
1% Ag/ZnO 3.40 88.0
1% Au/ZnO 3.93 89.3
2.2.2. TEM Characterization of the Catalysts. Representa-
tive transmission electron microscopy (TEM) images of 1%
Cu/ZnO, 1% Ag/ZnO, and 1% Au/ZnO catalysts recorded
after their use in the diesel soot oxidation cycle are presented
in Figures 2 and S1 (Supporting Information). As can be seen,
while after use in the diesel soot oxidation cycle, Au and Ag
NPs of average (ca.) size ∼90 nm are formed over the ZnO
surface, Cu NPs of wide size dispersion (10−140 nm size
range) were formed over the support. The average (ca.) size of
the Cu NPs was considerably smaller (∼53 nm) than the
average size of Au and Ag NPs (Table 1).
In Figure 2, we can also see that both the gold and silver
NPs are hemispherical in shape. These NPs are attached to the
support through their flatter planes over a specific crystal
orientation of the support crystallites. These images suggest
DOI: 10.1021/acsomega.8b03142
ACS Omega 2019, 4, 5795−5804
ACS Omega
Figure 2. Typical TEM images of the 1% Au/ZnO, 1% Ag/ZnO, and
1% Cu/ZnO catalysts.
that the interfaces between Au or Ag NPs and ZnO are in tight
contact (shown by white arrows).
2.2.3. Diffuse Reflectance Spectra of 1% Au/ZnO, 1% Ag/
ZnO, and 1% Cu/ZnO Catalysts. Figure 3 shows the UV−vis
Figure 3. UV−vis DRS absorption spectra of ZnO, 1% Cu/ZnO, 1%
Ag/ZnO, and 1% Au/ZnO. The band edge positions of the
composites are indicated by thick dotted dashed lines and the
maxima of the SPR absorption bands are indicated by continuous
arrows of respective colors.
diffuse reflectance spectra (DRS) of all the catalysts studied in
this investigation. Although the absorption spectrum of ZnO
revealed a low absorption in the visible spectral region with a
sharp absorption below 400 nm, the absorption in the visible
spectral region is high for all the three M/ZnO composites.
The broad absorption bands peaked around 450 and 510 nm
in the spectra of 1% Ag/ZnO and 1% Au/ZnO samples can be
associated with the surface plasmon resonance (SPR)
absorption of the Ag and Au NPs formed in the respective
composites.25−27 On the other hand, the absorption spectrum
of the 1% Cu/ZnO catalyst revealed a broad absorption signal
between 550 and 650 nm, corresponding to the SPR of
5797
Article
metallic Cu particles and a broad hump spreading through
400−510 nm associated with the absorption of Cu+.28 In
general, the onset of absorption edge for all the composite
catalysts remained close to 380 nm (Figure 3), which is close
to the absorption edge of the ZnO semiconductor.29 However,
linear fits to the sharp absorption sections of the spectra
revealed that their band gap energy differs slightly.
As can be noticed, the absorption band of the 1% Ag/ZnO
catalyst in the visible spectral range is exceptionally broad,
covering almost the whole part of the visible region (400−650
nm) with a maximum at around 450 nm, which might be the
result of overlapping the silver surface plasmonic resonance
signal with the σ−σ* and n−σ* transition signals of Agn
clusters, which appear in the 330−360 and 440−540 nm
spectral range, respectively.25,26 It is important to indicate that
the band at 275 nm attributed to Ag42+ (produced from the
dimerization of Ag2+) cannot be observed because of the
overlapping of the broad absorption signals spreading through
200 and 400 nm of ZnO.30,31
It is interesting to compare the absorption spectrum of pure
ZnO with the spectra of the supported catalysts. As can be
observed, the absorption edges of ZnO, 1% Cu/ZnO, 1% Ag/
ZnO, and 1% Au/ZnO are not superposed. Although the
absorption edge of the 1% Cu/ZnO and 1% Ag/ZnO catalysts
suffered a small shift toward lower wavelengths, the band edge
of the 1% Au/ZnO catalyst shifted toward higher wavelength.
These small shifts of band edge of the composite catalysts
can be explained by considering a probable interfacial
electronic interaction between the metals and the semi-
conductor support. The red shift (toward lower energy)
observed for the ZnO absorption edge in the 1% Au/ZnO
spectrum might be due to the electronic transfer from ZnO to
Au NPs at their interface. The blue shift (toward higher
energy) of the band edge detected for 1% Ag/ZnO and 1%
Cu/ZnO samples might be caused by the electron transfer
occurred from the Ag or Cu NPs to the ZnO support at their
interface. Although an increase in electron population in the
conduction band (CB) of ZnO effectively increases its band
gap due to the Burstein−Moss effect, the opposite can take
place due to decrease in electron population at the CB of the
semiconductor.32 These shifts are due to the interfacial
electronic interactions between the metals and ZnO. As the
interfacial area is a small region at the catalyst surface, the shifts
of the band edge are small, as expected. The results presented
in Figure 3 also suggest the presence of Cu, Ag, and Au in their
ionic and metallic states, which was supported by the results
obtained from the XPS analysis of the catalysts, presented in
the next section.
2.2.4. XPS Characterization of 1% Au/ZnO, 1% Ag/ZnO,
and 1% Cu/ZnO Catalysts. The capability of a catalyst to
activate oxygen is closely associated with its activity in
oxidation reactions. The electronic states of Cu, Ag, and Au
supported on ZnO were determined by XPS to determine the
possible interactions between the catalysts and oxygen during
oxidation reactions. The binding energies (BEs) for the core
electrons and estimated metal/Zn atomic ratios of the catalysts
are presented in Table 2.
2.2.4.1. 1% Cu/ZnO Catalyst. The identification of both
Cu+ and Cu0 copper species in solid catalysts is difficult from
XPS analysis alone. The BEs of the Cu 2p3/2 core-level
emissions from Cu+ and Cu0 are essentially the same and are
detected at about 1.4 eV below that of Cu2+ ions.33 Therefore,
we analyzed their L3VV X-ray-induced Auger emissions (AEs)
DOI: 10.1021/acsomega.8b03142
ACS Omega 2019, 4, 5795−5804
ACS Omega Article

Table 2. BEs of the Components and Surface Metal/Zn

Atomic Ratio of the Catalystsa
catalyst metal BE (eV) Zn 2p3/2 (eV) atomic ratio metal/Zn
1% Au/ZnO Au 4f7/2
83.4 (7) 1021.8 0.19
85.6 (9)
88.0 (84)
1% Ag/ZnO Ag 3d5/2
367.3 (80) 1021.8 0.26
368.3 (20)
1% Cu/ZnO Cu αA
1849.2 (90) 1020.8 0.38
1851.0 (10)
a
The % peak area of the components are presented in parentheses.

to identify Cu+ and Cu0 in the 1% Cu/ZnO catalyst. The

Auger parameter (αA) was defined as
αA = hν + (BE Cu 2p3/2 − BE Cu L3VV )
where hν is the energy of the incident photon (1253.6 eV), BE
Cu 2p3/2 is the BE of the Cu 2p3/2 photoelectron, and BE
CuL3VV is the L3VV Auger emission.
The CuL3VV Auger spectrum of 1% Cu/ZnO is dominated by
the ZnL3VV Auger peaks that appeared in the same energy
region as of CuL3VV. Nevertheless, the peak fitting procedure
allowed us to determine the CuL3VV contribution. In Figure 4,
(1)
Figure 5. XPS spectrum of 1% Ag/ZnO.
However, the catalyst was reduced during its preparation in
pure H2 at high temperature, suggesting the presence of Ag0 at
the surface of the catalyst. Now, the enthalpy of formation of
bulk Ag2O (−ΔHf = 7 kcal/mol) is very low. This value
indicates that the surface oxidation of Ag0 to Ag2O is hardly
possible under the present reduction conditions, or even in
higher temperatures of oxidation conditions.39 Notwithstand-
ing, the XPS analysis revealed a high percentage of Ag+ after
catalyst reduction.
2.2.4.3. 1% Au/ZnO Catalyst. From the XPS analysis results
of sample 1% Au/ZnO presented in Figure 6 and Table 2, we

Figure 4. CuL3VV Auger transition of 1% Cu/ZnO.

the core-level spectrum of the sample is presented. In Table 2,

the BEs of Zn 2p3/2 and Cu 2p3/2 levels, the values of αA, and
the Cu/Zn atomic ratios in the catalyst are presented.
2.2.4.2. 1% Ag/ZnO Catalyst. The XPS spectrum of 1% Ag/
ZnO is displayed in Figure 5. The XPS estimated that the Ag/
Zn atomic ratio (presented in Table 2) is about 0.26. As it has
been listed in Table 2, the Ag 3d5/2 emission band comprises
two components. The component located at around 367.3 eV
corresponds to Ag+ and the component at 368.3 eV
corresponds to Ag0 electronic states.34−38 Our analysis
revealed a high amount of Ag+ at the surface of the catalyst.
5798
Figure 6. XPS spectrum of 1% Au/ZnO.
can see that the XPS spectrum of the catalyst revealed the Au
4f7/2 emission band with three components. These compo-
nents are located at around 83.4, 85.6, and 88.0 eV and
correspond to Au 0 , Au + , and Au 3+ electronic states,
respectively. The analysis revealed high amounts of Au3+
(84%) with minor contributions of Au0 and Au+. The Au/Zn
atomic ratio value at the surface of the catalyst (Table 2) is
DOI: 10.1021/acsomega.8b03142
ACS Omega 2019, 4, 5795−5804
ACS Omega Article

about 0.19 only. This value indicates a low metal dispersion reduced during its preparation in pure H2 at high temperature,
and the formation of gold NPs of high average particle size, justifying the presence of Au0 at the surface of the catalyst.
supporting the observation made from the TEM micrograph of Moreover, TEM results revealed the presence of large Au
the sample (Figure 2). particles at the catalyst surface, which should behave as bulk
2.2.5. Metal−Support Interactions in 1% Cu/ZnO, 1% Ag/ gold, which is rarely found in oxidized state. Now, as the 1%
ZnO, and 1% Au/ZnO Catalysts. The XPS analysis of Au/ZnO catalyst was prepared using NaAuCl4 solution,
electronic states of Cu, Ag, and Au in the catalysts revealed chloride traces might have remained despite the H2 reduction
the presence of metallic and ionic species at their surfaces. The at 450 °C. The presence of AuCl3 also cannot be discarded,
presence of these species can be explained by considering the which would be responsible for the Au3+ contribution at the
energy level alignment concept, correlating the interactions of catalyst surface. However, at the ZnO−Au interfacial region,
Cu, Ag, or Au at the interface with ZnO, which is an n-type the electron transfer from ZnO to Au might have resulted in
semiconductor. the formation of metallic Au, despite the interactions between
The work function values of ZnO, Au, Ag, and Cu are gold and chloride in other regions of the catalyst.
presented in Table 3. ZnO presents a work function value of The results obtained from the DRS spectra of the composite
catalysts (Figure 2) support these assumptions. The electronic
Table 3. Work Function Values of the Different Compounds transfer from copper and silver to ZnO might have generated
in the Catalysts an enrichment of electrons in ZnO support, which might have
resulted in the blue shift of its band gap energy. On the other
compound work function (eV)
hand, the electron transfer from ZnO to gold might have
ZnO 4.9 generated a decrease in the electronic density of interfacial
Cu 4.6
ZnO molecules, resulting in the red shift of its band gap
Cu+ 4.9
observed in the absorption spectrum of 1% Au/ZnO.
Cu2+ 5.9
2.3. Diesel Soot Oxidation on the Catalysts. Gen-
Ag 4.2
eration of CO during diesel soot oxidation reactions was not
Ag+ 5.3
detected in the studied soot oxidation conditions of this
Au 5.1
investigation (25−600 °C, 20 vol % O2), which might be due
Au+
to the high oxidation activity of 1% Cu/ZnO, 1% Ag/ZnO, and
Au3+
1% Au/ZnO catalysts. The CO oxidation rate might have been
higher than the CO generation rate during soot oxidation over
4.9 eV, which is higher than that of metallic Cu (4.6 eV) and the catalysts. Indeed, these results show that the diesel soot
metallic Ag (4.26 eV). Because of the energy level alignment, reacts predominantly via the combustion reaction at the very
the Fermi level of Cu and Ag remains at higher level than that strong oxidation conditions in which the reaction is performed
of ZnO. Therefore, when in contact, the electrons migrate (20 vol % of O2). Nevertheless, the evolutions of diesel soot
from copper or silver to the CB of ZnO at their interface, to oxidation over ZnO at 25−800 °C revealed only trace amounts
achieve the Fermi level equilibration. The electron migration of CO at about 500 °C.
process causes a reduction in the stability of metallic copper or The CO2 evolutions during the diesel soot oxidation with
metallic silver at the metal−support interface.40,41 As revealed temperature over the three catalysts studied are displayed in
by XPS analysis (Table 2), the formation of Cu+ or Ag+ results Figure 7. From these curves, the Tinitial (temperatures at which
from the electron transfer from metallic Cu or Ag to ZnO at the oxidation started), Tmax (temperatures when the oxidation
the metal−support interface. As can be observed in Table 3, reached a maximum), and Tfinal (temperatures when the
although about 10% of Cu+ was revealed at the 1% Cu/ZnO
surface, the presence of about 80% Ag+ was revealed at the
surface of the 1% Ag/ZnO catalyst. The strong difference
between Cu+ and Ag+ surface concentrations may be due to
the work function differences of Cu and Ag (Table 3). Indeed,
Ag presenting a lower work function value (4.2 eV) than that
of Cu (4.6 eV) has a higher value of its Fermi level energy than
that of Cu. The transfer of electrons from Cu to ZnO until the
two systems attain equilibrium for the new Fermi level to be
established may be lower than the transfer of electrons from Ag
to ZnO, resulting in a higher concentration of Ag+ compared
with the Cu+ concentration at the surface of the catalysts.
The work function of Au (5.1 eV) is a bit higher than that of
ZnO (4.9 eV). Therefore, the Fermi level of ZnO remains at a
bit higher energy than that of gold. In this case, the electrons
will migrate from the CB of ZnO to Au at their interface to
achieve the Fermi level equilibration when they are in contact.
The Fermi level equilibration increases the stability of metallic
gold at the Au−ZnO interface.40,41 The formation of very
stable metallic Au0 results from the electron transfer from ZnO
to Au as revealed by XPS (Table 2).
XPS analysis revealed high amounts of Au3+ (84%) with Figure 7. Evolution of CO2 as a function of temperature during diesel
minor contributions of Au0 and Au+. However, the catalyst was soot oxidation over the catalysts.

5799 DOI: 10.1021/acsomega.8b03142

ACS Omega 2019, 4, 5795−5804
ACS Omega Article

Table 4. Integrated Areas under CO2 Evolution ([CO2]Cat), [CO2]Cat/[CO2]ZnO Ratios, and Tinitial, Tmax, and Tfinal for the
Catalysts During the Diesel Soot Oxidation
catalyst [CO2]Cat (1018 molecules °C) [CO2]Cat/[CO2]ZnO Tinitial Tmax Tfinal
temperatures (°C)
ZnO 845a 1.00 225 >600 >600
1% Cu/ZnO 634 0.74 100 250 450
1% Ag/ZnO 542 0.63 75 205 325
1% Au/ZnO 841 0.99 95 225 450
a
Calculated from 25 to 800 °C.

reaction completed) were calculated for the three catalysts and consisting of neighboring Au0 and Au3+ (Au0−Au3+). The
presented in Table 4. As can be noticed from Figure 7 and Au0 sites may be located at the Au/ZnO interface and the Au3+
Table 4, the diesel soot oxidation activity of all the three site at the gold NP surface, in close proximity to Au0 (Figure
catalysts takes place at temperatures <400 °C. 8). This site might have facilitated the diesel soot oxidation
In Figure 7, CO2 evolution during diesel soot oxidation following a Langmuir−Hinshelwood reaction mechanism,
deposited over reference ZnO in between 25 and 800 °C is according to the following steps:
presented. In these reaction conditions, the total area under
the CO2 evolution curve from 25 to 800 °C ([CO2]ZnO) was
used as a measurement of the highest amount of carbon in the
diesel soot, which was accumulated over the catalysts for 1 h.
To compare the catalytic activity of our three catalysts, the
areas under the CO2 evolution curves, during the diesel soot
oxidation over the catalysts ([CO2]Cat), were estimated and
compared with [CO2]ZnO. The calculated values of [CO2]Cat
and [CO2]Cat/[CO2]ZnO are reported in Table 4. In the table, it
can be seen that [CO2]Au/[CO2]ZnO (calculated for 1% Au/
ZnO) attained the highest value compared with the calculated
values for 1% Cu/ZnO and 1% Ag/ZnO. These results
indicate that 1% Au/ZnO is a very active and superior catalyst
for diesel soot oxidation. The appearance of intense and sharp
signal (Figure 7) in 200−300 °C temperature range, with a
peak at 230 °C, indicates that the diesel soot deposited during
diesel combustion is probably fully oxidized at this low
temperature.
2.3.1. Mechanistic Considerations of Diesel Soot Oxida-
tion over the Catalysts. The differences in the activities
presented by 1% Cu/ZnO, 1% Ag/ZnO, and 1% Au/ZnO for Figure 8. Proposed catalytic site model at the Au/ZnO surface.
diesel soot oxidation cannot be explained by the estimated
specific surface area of the catalysts. As can be seen in Table 1,
all the three catalysts present a similar specific surface area. On 2.3.1.1. First Step. At the Au/ZnO interface, O2 was
the other hand, the diesel soot oxidation activities of the adsorbed on the Au0 moiety of the catalytic site (Au0−Au3+)
catalysts (Figure 7 and Table 4) cannot be explained neither by and superoxide ions (O2−) were generated. Superoxide species
the differences in the average metal NP size in them. Although are very active species for optimizing the oxidation of diesel
the TEM images of 1% Ag/ZnO and 1% Au/ZnO (Figure 2) soot.42−47
revealed the formation of metal NPs of very similar (∼88 nm 2.3.1.2. Second Step. The second step involves simulta-
for Ag and 89 nm for Au) average sizes in the composite neous adsorption of diesel soot at the Au3+ moiety of the
catalysts, the gold-supported catalyst manifests much higher catalytic site. The probability of the diesel soot adsorption
diesel soot oxidation activity. On the other hand, the 1% Cu/ occurrence on the catalyst surface will increase with the
ZnO catalyst, containing metallic NPs of about 53 nm average number of activated diesel soot molecules striking the surface.
size, presents the same behavior as 1% Ag/ZnO catalyst. The striking molecules, to be adsorbed, must carry a total
The catalytic behavior of the three catalysts cannot be energy equal to or greater than the adsorption activation
explained by the metal surface atomic concentration revealed energy. The total energy ET of the diesel soot particle is
by XPS (Table 2). It can be seen that the relative atomic ratio considered to be the sum of its kinetic energy EK (defined by
(M/Zn) decreases in the order: Cu > Ag > Au. However, the the kinetic theory of gases) plus its potential energy UC
[CO2]Cat/[CO2]ZnO ratio shown in Table 4 decreases in the (generated by the Coulombic forces between the π electrons
order: Au > Cu > Ag. of the CC bonds present in the diesel soot molecules and
Therefore, to explain the exceptionally high diesel soot the Au3+ moiety of the catalytic site), according to the
oxidation activity of 1% Au/ZnO at low temperature in following equation:
comparison to 1% Cu/ZnO and 1% Ag/ZnO, it is convenient E T = E K + UC (2)
to explain first the effects of 1% Au/ZnO on the oxidation
reaction. On the basis of the results of XPS analysis of the The total energy of the diesel soot particles being adsorbed
catalyst surface, we propose a bifunctional catalytic site at the Au3+ moiety can be expressed as
5800 DOI: 10.1021/acsomega.8b03142
ACS Omega 2019, 4, 5795−5804
ACS Omega
3 e2
E T Au = kBT + 3kc
2 r
where kB is the Boltzmann constant, T is the absolute
temperature, 3 stands for the charge number (oxidation state)
of Au3+, kc is the Coulomb constant, e is the electric charge,
and r is the distance between the charges.
2.3.1.3. Third Step. Reaction of the H−C bond of the
adsorbed diesel soot molecule at the Au3+ moiety with the
superoxide formed at Au0. This step may result in the
abstraction of H atoms by the very active superoxide ions. The
reaction between the superoxides formed over Au0 with the
adsorbed diesel soot at Au3+ would strongly increase the rate of
diesel soot oxidation. The successive, simultaneous interactions
of H−C bonds of the diesel soot molecule with O2− at the
catalyst surface may result in the generation of CO2 and H2O
molecules (as the final products) at low oxidation temperature.
For 1% Cu/ZnO and 1% Ag/ZnO, based on their XPS
analysis, we propose a similar catalytic site model at the
catalyst surface (Figures 9 and 10), involving Cu+ or Ag+ at the
Figure 9. Proposed catalytic site model at the Cu/ZnO surface.
Figure 10. Proposed catalytic site model at the Ag/ZnO surface.
Cu/ZnO or Ag/ZnO interfaces, and surface Cu0 or Ag0 sites in
proximity to Cu+ or Ag+. Developed bifunctional catalytic sites
consisting of [Cu+−Cu0] or [Ag+−Ag0] would facilitate the
particle matter oxidation following a similar mechanism at the
bifunctional [Au0−Au3+] site.
Article
However, the adsorption rate of diesel soot at the Cu+ or
Ag+ moieties of the proposed catalytic sites (step 2) would be
(3)
much lower than the adsorption rate at the Au3+ moieties of
the catalytic sites of 1% Au/ZnO. To provide a mathematical
justification of such assumption, we calculated the total energy
ET value of each diesel soot molecule striking the catalytic sites
of copper or silver catalysts:
3 e2
E T Cu = kBT + 1kc
2 r (4)
3 e2
E T Ag = kBT + 1kc
2 r (5)
The number 1 in eqs 4 and 5 stands for the electronic charge
of Cu+ and Ag+, respectively.
However, for the same temperature,
E T Au > E T Cu (6)
E T Au > E T Ag (7)
because of the higher oxidation state of Au3+.
The diesel soot particles, reacting on the Au3+ moieties, may
attain the required adsorption activation energy at higher rates
than on Cu+ or Ag+, resulting in a higher adsorption rate,
which is the determining reaction step for diesel soot
oxidation.
3. CONCLUSIONS
In summary, the results obtained on the IB group metal-
supported ZnO suggest that the diesel soot oxidation activity
of metal-supported metal oxide catalysts is determined by the
presence of a metal catalytic site involving M0−Mδ+ moieties.
Although the M0 moieties accelerate the generation of a
superoxide, the Mδ+ moieties accelerate the diesel soot
adsorption process. The diesel soot adsorption, which is the
rate-determining step in diesel soot oxidation process, can be
accelerated by increasing its Coulombic potential energy,
generated by the Coulombic forces between the π electrons of
the CC bonds present in the diesel soot molecules and the
ionic metal species Mδ+ on the metal NPs. Therefore, the diesel
soot oxidation activity of the supported catalysts depends on
the number of electric charges of metal ion moieties, which
reside at the catalyst surface. We demonstrate the effect of
electronic state(s) of metals in metal-supported semiconduct-
ing catalysts on their diesel soot oxidation ability. The
proposed general model can also be extended to other
metal−semiconductor heterogeneous oxidation catalysts.
However, we must recognize that the oxidation state of the
supported metal over a semiconductor support depends
considerably on the process of their fabrication/synthesis.
4. EXPERIMENTAL SECTION
4.1. Catalysts Preparation. The support used for the
preparation of the catalysts was ZnO powder, supplied by
Aldrich (99.99%). The catalysts were prepared by impregna-
tion, using the required amounts of aqueous Cu(NO3)2
(Aldrich 99.99%), AgNO3 (Aldrich 99.99%), and NaAuCl4
(Aldrich 99.99%) solutions to obtain 1 wt % M/ZnO mixtures
(M = Cu, Ag, or Au). The suspensions were magnetically
stirred at 25 °C for 1 h. The catalysts were recovered by
filtration, washed thoroughly to remove unreacted species
(soluble sodium and chlorine), and dried under magnetic
5801 DOI: 10.1021/acsomega.8b03142
ACS Omega 2019, 4, 5795−5804
ACS Omega
stirring at 120 °C overnight. The resulting powders were
reduced under pure H2 at a volume flow rate of 80 mL min−1
at 450 °C for 4 h. The temperature of the furnace was
increased at the rate of 10 °C min−1. The catalysts were cooled
down to 25 °C under H2 flow, after which the samples were
purged with a nitrogen flow for 30 min. The catalysts were
then stored in dry conditions and designated as 1% Cu/ZnO,
1% Ag/ZnO, and 1% Au/ZnO. A ZnO sample was prepared in
the same way to use as the reference.
4.2. Catalyst Characterization. The N2 adsorption−
desorption isotherms of the catalysts were measured using a
BELSORP Mini-II (BEL, Japan) sorptometer, after degas-
ification at 400 °C for 2 h. The specific surface area (Sg) of the
catalysts was determined from their N2 physisorptions at −196
°C, using Brunauer−Emmett−Teller analysis. The isotherms
were recorded in the pressure range 0.0−6.6 kPa. The
saturation uptake was determined using the technique of
back extrapolation of the linear portion of the isotherms to
zero equilibrium pressure.
A Shimadzu UV−vis spectrophotometer equipped with an
integrating sphere was used to obtain the DRS of the catalysts,
using BaSO4 as the standard reflectance sample.
XPS spectra were recorded on freshly prepared 1% Cu/ZnO,
1% Ag/ZnO, and 1% Au/ZnO samples using an ESCALAB
200R electron spectrometer equipped with a hemispherical
analyzer, operating in a constant pass energy mode. For
recording the XPS spectra of the catalysts, a monochromatic
Mg Kα emission (hν = 1253.6 eV) from the X-ray tube
operating at 10 mA and 12 kV was utilized. To get good signal-
to-noise ratios, the energy regions of the photoelectrons of
interest were scanned a number of times. The intensities of the
emission peaks were determined by integrating the area under
each peak after subtracting an S-shaped background and fitting
the experimental peak to Lorentzian/Gaussian curves (80% L/
20% G). Utilizing the position of C 1s signal, coming from
adventitious carbon, which appeared around 284.9 ± 0.2 eV,
the peak positions of the elements were referenced.
TEM (JEM 2100F microscope fitted with an INCA X-sight,
Oxford Instruments), operating at 200 kV accelerating voltage
and line resolution of 0.14 nm, was used to characterize the
Cu, Ag, and Au particle sizes for each catalyst. Before the TEM
analysis, the catalyst samples were ground and suspended in
ethanol. A drop of the suspension was then mounted over a
carbon-coated copper grid and the solvent was evaporated.
The periodic images of the structures on the electron
micrographs were analyzed using digital Fourier trans-
formation.
4.3. Generation of Diesel Soot. In Figure 11, the
schematics of the system used for generating a diesel soot is
presented. Pure Mexican diesel was burned in a glass vessel
(diesel burner) under an air flow rate of 100 mL min−1 for 1 h.
In this investigation, for referring both the soluble and
insoluble fractions of the diesel emission, the term “diesel
soot” is used.
The diesel combustion emission from the exhaust of the
vessel was directed to the catalyst sample, which was placed in
a tubular quartz reactor with an inner diameter of 1 cm. The
reactor was placed in a programmable furnace, as shown in
Figure 11. The resulting contact between the diesel soot
generated in the glass vessel and the catalyst is considered
similar to the contact between the diesel soot generated from a
real diesel engine and the catalyzed soot filter. Therefore, the
concept of light mode or tight mode contact between the
5802
Article
Figure 11. Diagram of the system used for studying the generation
and catalytic oxidation of diesel soot process. (1) Air; (2) diesel
burner; (3) reactor in a programmable furnace; (4) temperature
controller; and (5) gas chromatograph.
diesel soot and the catalyst used in several research studies
cannot be applied here.
A Bruker FT-IR spectrometer (Vertex 70) operating in the
800−4000 cm−1 spectral range was used for the character-
ization of the soot generated during diesel combustion in the
glass vessel. The diesel combustion emissions were accumu-
lated on ZnO for 1 h under the same conditions. The FT-IR
spectrum was recorded using a thin, uniform KBr pellet
prepared with 0.2 wt % of the diesel soot/ZnO mixture.
4.4. Diesel Soot Oxidation through Temperature-
Programmed Experiments. The performance of 1% Cu/
ZnO, 1% Ag/ZnO, and 1% Au/ZnO catalysts for diesel soot
oxidation was evaluated by temperature-programmed oxidation
of the diesel soot/catalyst mixtures. For this purpose, after the
diesel soot accumulation over the catalyst, weakly attached
combustion products were removed by air (20 vol % of O2 and
80 vol % of N2) flow of 100 mL min−1. This flow was
maintained during the entire soot oxidation process. The diesel
soot/catalyst mixture was then heated from 25 to 600 °C at a
heating rate of 5 °C min−1.
In order to monitor the reaction temperature along with the
exothermic heat of the diesel soot oxidation, a thermocouple
was inserted into the diesel soot−catalyst mixture. The diesel
soot oxidation products from the reactor were analyzed every
10 min using a Shimadzu gas chromatograph provided with a
thermo-conductivity detector to monitor the CO and CO2
evolution at different temperatures. To determine the catalytic
effect, diesel soot oxidation was performed under the same
conditions using diesel soot/ZnO mixture as the reference at
temperatures between 25 and 800 °C.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsome-
ga.8b03142.
High-resolution TEM images of 1% Au/ZnO (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: griselda.corro@correo.buap.mx. Phone: +52 22
2295500-7294 (G.C.).
DOI: 10.1021/acsomega.8b03142
ACS Omega 2019, 4, 5795−5804
ACS Omega
ORCID
Grisel Corro: 0000-0002-7645-4477
Umapada Pal: 0000-0002-5665-106X
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge Vicerrectoria de Investigación y
Estudios de Posgrado BUAP (Proyect # 69-2018) and
Secretariá de Energia-Consejo
́ Nacional de Ciencia y
Tecnologiá (Cluster Biodiesel Avanzado
FSE 250014),
Mexico, for their financial support.
■
REFERENCES
(1) Bueno-López, A. Diesel soot combustion ceria catalysts. Appl.
Catal., B 2014, 146, 1−11.
(2) Krishna, K.; Bueno-López, A.; Makkee, M.; Moulijn, J. A.
Potential rare earth modified CeO2 catalysts for soot oxidation: I.
Characterisation and catalytic activity with O2. Appl. Catal., B 2007,
75, 189−200.
(3) Zokoe, J.; McGinn, P. J. Catalytic diesel soot oxidation by
hydrothermally stable glass catalysts. Chem. Eng. J. 2015, 262, 68−77.
(4) Atribak, I.; Bueno-López, A.; García-García, A. Uncatalysed and
catalysed soot combustion under NOx+O2: Real diesel versus model
soots. Combust. Flame 2010, 157, 2086−2094.
(5) Hinot, K.; Burtscher, H.; Weber, A.; Kasper, G. The effect of the
contact between platinum and soot particles on the catalytic oxidation
of soot deposits on a diesel particle filter. Appl. Catal., B 2007, 71,
271−278.
(6) Fino, D.; Specchia, V. Open issues in oxidative catalysis for diesel
particulate abatement. Powder Technol. 2008, 180, 64−73.
(7) Lepperhoff, G.; Lüders, H.; Barthe, P.; Lemaire, J. Quasi-
Continuous Particle Trap Regeneration by Cerium-Additives; SAE
International, 1995.
(8) Allansson, R.; Blakeman, P. G.; Cooper, B. J.; Hess, H.; Silcock,
P. J.; Walker, A. P. Optimizing the Low Temperature Performance and
Regeneration Efficiency of the Continuously Regenerating Diesel
Particulate Filter (CR-DPF) System; SAE International, 2002.
(9) Setiabudi, A.; van Setten, B. A. A. L.; Makkee, M.; Moulijn, J. A.
The influence of NOx on soot oxidation rate: molten salt versus
platinum. Appl. Catal., B 2002, 35, 159−166.
(10) Reichert, D.; Finke, T.; Atanassova, N.; Bockhorn, H.; Kureti,
S. Global kinetic modelling of the reaction of soot with O2 and NOx
on Fe2O3 catalyst. Appl. Catal., B 2008, 84, 803−812.
(11) Sun, M.; Wang, L.; Feng, B.; Zhang, Z.; Lu, G.; Guo, Y. The
role of potassium in K/Co3O4 for soot combustion under loose
contact. Catal. Today 2011, 175, 100−105.
(12) Hueso, J.; Caballero, A.; Ocana, M.; Gonzalezelipe, A.
Reactivity of lanthanum substituted cobaltites toward carbon particles.
J. Catal. 2008, 257, 334−344.
(13) Atribak, I.; Bueno-López, A.; García-García, A.; Navarro, P.;
Frías, D.; Montes, M. Catalytic activity for soot combustion of
birnessite and cryptomelane. Appl. Catal., B 2010, 93, 267−273.
(14) Zouaoui, N.; Issa, M.; Kehrli, D.; Jeguirim, M. CeO2 catalytic
activity for soot oxidation under NO/O2 in loose and tight contact.
Catal. Today 2012, 189, 65−69.
(15) Liu, J.; Zhao, Z.; Xu, C.-m.; Duan, A.-j. Simultaneous removal
of NOx and diesel soot over nanometer Ln-Na-Cu-O perovskite-like
complex oxide catalysts. Appl. Catal., B 2008, 78, 61−72.
(16) Yamazaki, K.; Sakakibara, Y.; Dong, F.; Shinjoh, H. The remote
oxidation of soot separated by ash deposits via silver-ceria composite
catalysts. Appl. Catal., A 2014, 476, 113−120.
(17) Lee, C.; Park, J.-I.; Shul, Y.-G.; Einaga, H.; Teraoka, Y. Ag
supported on electrospun macro-structure CeO2 fibrous mats for
diesel soot oxidation. Appl. Catal., B 2015, 174−175, 185−192.
(18) Liu, S.; Wu, X.; Liu, W.; Chen, W.; Ran, R.; Li, M.; Weng, D.
Soot oxidation over CeO2 and Ag/CeO2: Factors determining the
5803
Article
catalyst activity and stability during reaction. J. Catal. 2016, 337, 188−
198.
(19) Corro, G.; Cebada, S.; Pal, U.; Fierro, J. L. G.; Alvarado, J.
Hydrogen-reduced Cu/ZnO composite as efficient reusable catalyst
for diesel particulate matter oxidation. Appl. Catal., B 2015, 165, 555−
565.
(20) Corro, G.; Vidal, E.; Cebada, S.; Pal, U.; Bañuelos, F.; Vargas,
D.; Guilleminot, E. Electronic state of silver in Ag/SiO2 and Ag/ZnO
catalysts and its effect on diesel particulate matter oxidation: An XPS
study. Appl. Catal., B 2017, 216, 1−10.
(21) Corro, G.; Cebada, S.; Pal, U.; Fierro, J. L. G. Au0−Au3+
bifunctional site mediated enhanced catalytic activity of Au/ZnO
composite in diesel particulate matter oxidation. J. Catal. 2017, 347,
148−156.
(22) Salamanca, M.; Mondragón, F.; Agudelo, J. R.; Benjumea, P.;
Santamaría, A. Variations in the chemical composition and
morphology of soot induced by the unsaturation degree of biodiesel
and a biodiesel blend. Combust. Flame 2012, 159, 1100−1108.
(23) Bellamy, L. J. The Infrared Spectra of Complex Molecules, 3rd ed.;
Chapman and Hall Ltd.: London, 1975.
(24) Sarbak, Z. Characterization and infrared study of the effect of
Cr, Mo and W on carbon deposition on platinum/alumina. Appl.
Catal., A 1999, 177, 85−97.
(25) Ozin, G. A.; Huber, H. Cryophotoclustering techniques for
synthesizing very small, naked silver clusters Agn of known size (where
n = 2-5). The molecular metal cluster-bulk metal particle interface.
Inorg. Chem. 1978, 17, 155−163.
(26) McIntosh, D.; Ozin, G. A. Synthesis using metal vapors. Silver
carbonyls. Matrix infrared, ultraviolet-visible, and electron spin
resonance spectra, structures, and bonding of silver tricarbonyl, silver
dicarbonyl, silver monocarbonyl, and disilver hexacarbonyl. J. Am.
Chem. Soc. 1976, 98, 3167−3175.
(27) Kowalska, E.; Mahaney, O. O. P.; Abe, R.; Ohtani, B. Visible-
light-induced photocatalysis through surface plasmon excitation of
gold on titania surfaces. Phys. Chem. Chem. Phys. 2010, 12, 2344−
2355.
(28) Tan, Z. Y.; Yong, D. W. Y.; Zhang, Z.; Low, H. Y.; Chen, L.;
Chin, W. S. Nanostructured Cu/ZnO Coupled Composites: Toward
tunable Cu nanoparticle sizes and plasmon absorption. J. Phys. Chem.
C 2013, 117, 10780−10787.
(29) Hu, Y.; Chen, H.-J. Preparation and characterization of
nanocrystalline ZnO particles from a hydrothermal process. J.
Nanopart. Res. 2007, 10, 401−407.
(30) Linnert, T.; Mulvaney, P.; Henglein, A.; Weller, H. Long-lived
nonmetallic silver clusters in aqueous solution: preparation and
photolysis. J. Am. Chem. Soc. 1990, 112, 4657−4664.
(31) Ershov, B. G.; Janata, E.; Michaelis, M.; Henglein, A. Reduction
of aqueous copper(2+) by carbon dioxide(1-): first steps and the
formation of colloidal copper. J. Phys. Chem. 1991, 95, 8996−8999.
(32) Grundmann, M. The Physics of Semiconductors, 3rd ed.; Springer
International Publishing: New York, 2016; Vol. 3, pp XXXIX−989.
(33) Singh, S. C.; Gopal, R. Zinc nanoparticles in solution by laser
ablation technique. Bull. Mater. Sci. 2007, 30, 291−293.
(34) Richter, M.; Langpape, M.; Kolf, S.; Grubert, G.; Eckelt, R.;
Radnik, J.; Schneider, M.; Pohl, M. M.; Fricke, R. Combinatorial
preparation and high-throughput catalytic tests of multi-component
deNOx catalysts. Appl. Catal., B 2002, 36, 261−277.
(35) Hoflund, G. B.; Hazos, Z. F.; Salaita, G. N. Surface
characterization study of Ag, AgO, and Ag2O using x-ray photo-
electron spectroscopy and electron energy-loss spectroscopy. Phys.
Rev. B: Condens. Matter Mater. Phys. 2000, 62, 11126−11133.
(36) She, X.; Flytzanistephanopoulos, M. The role of AgOAl species
in silver-alumina catalysts for the selective catalytic reduction of NOx
with methane. J. Catal. 2006, 237, 79−93.
(37) Lu, W.; Gao, S.; Wang, J. One-Pot Synthesis of Ag/ZnO self-
assembled 3D hollow microspheres with enhanced photocatalytic
performance. J. Phys. Chem. C 2008, 112, 16792−16800.
DOI: 10.1021/acsomega.8b03142
ACS Omega 2019, 4, 5795−5804
ACS Omega Article

(38) Balachandran, S.; Selvam, K.; Babu, B.; Swaminathan, M. The

simple hydrothermal synthesis of Ag−ZnO−SnO2 nanochain and its
multiple applications. Dalton Trans. 2013, 42, 16365−16374.
(39) Fein, D.; Wachs, I. E. Quantitative determination of the
catalytic activity of bulk metal oxides for formic acid oxidation. J.
Catal. 2002, 210, 241−254.
(40) Lin, D.; Wu, H.; Zhang, R.; Pan, W. Enhanced Photocatalysis of
Electrospun Ag−ZnO Heterostructured Nanofibers. Chem. Mater.
2009, 21, 3479−3484.
(41) Han, Z.; Ren, L.; Cui, Z.; Chen, C.; Pan, H.; Chen, J. Ag/ZnO
flower heterostructures as a visible-light driven photocatalyst via
surface plasmon resonance. Appl. Catal., B 2012, 126, 298−305.
(42) Villani, K.; Brosius, R.; Martens, J. Catalytic carbon oxidation
over Ag/Al2O3. J. Catal. 2005, 236, 172−175.
(43) Aneggi, E.; Llorca, J.; de Leitenburg, C.; Dolcetti, G.; Trovarelli,
A. Soot combustion over silver-supported catalysts. Appl. Catal., B
2009, 91, 489−498.
(44) Guzman, J.; Carrettin, S.; Fierro-Gonzalez, J. C.; Hao, Y.;
Gates, B. C.; Corma, A. CO oxidation catalyzed by supported gold:
cooperation between gold and nanocrystalline rare-earth supports
forms reactive surface superoxide and peroxide species. Angew. Chem.,
Int. Ed. 2005, 44, 4778−4781.
(45) Wei, Y.; Zhao, Z.; Liu, J.; Liu, S.; Xu, C.; Duan, A.; Jiang, G.
Multifunctional catalysts of three-dimensionally ordered macroporous
oxide-supported Au@Pt core-shell nanoparticles with high catalytic
activity and stability for soot oxidation. J. Catal. 2014, 317, 62−74.
(46) Silva, C. G.; Sampaio, M. J.; Carabineiro, S. A. C.; Oliveira, J.
W. L.; Baptista, D. L.; Bacsa, R.; Machado, B. F.; Serp, P.; Figueiredo,
J. L.; Silva, A. M. T.; Faria, J. L. Developing highly active
photocatalysts: Gold-loaded ZnO for solar phenol oxidation. J.
Catal. 2014, 316, 182−190.
(47) Liu, X.; Liu, M.-H.; Luo, Y.-C.; Mou, C.-Y.; Lin, S. D.; Cheng,
H.; Chen, J.-M.; Lee, J.-F.; Lin, T.-S. Strong Metal-Support
Interactions between Gold Nanoparticles and ZnO Nanorods in
CO Oxidation. J. Am. Chem. Soc. 2012, 134, 10251−10258.

5804 DOI: 10.1021/acsomega.8b03142

ACS Omega 2019, 4, 5795−5804